Mercerizing solutions

ABSTRACT

Aqueous mercerizing solutions containing alkali metal hydroxide and 0.1 to 5 g/l of a phosphonic acid derivative of the formula   IN WHICH R is aliphatic hydrocarbon radical and X and Y each is hydrogen, an alkali metal ion or a lower aliphatic radical, and the use of these solutions in a process for mercerizing cellulose fibrous material..

United States Patent [1 1 Diery et al.

1 MERCERlZlNG SOLUTIONS [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: June 21, 1973 [21] Appl. No.: 372,391

[30] Foreign Application Priority Data June 26, 1972 Germany 2231148 [52] US. Cl 8/127; 8/125 [51] Int. Cl D06m 1/02 [58] Field of Search 8/127, 116 P, 125

[56] References Cited UNITED STATES PATENTS 4/1943 V012 11/1934 Kern 8/127 1 June 17, 1975 2,236,617 4/1941 Brandt 1, 8/127 2,403,038 7/1946 Aelony 8/127 2,478,390 8/1949 Hanford ct al U 260/459 Primary Examiner-Benjamin R. Padgett Assistant Examiner-B. Hunt Attorney, Agent, or Firm-Connolly and Hutz [57} ABSTRACT Aqueous mercerizing solutions containing alkali metal hydroxide and 0.1 to 5 g/l of a phosphonic acid derivative of the formula o/ox in which R is aliphatic hydrocarbon radical and X and Y each is hydrogen, an alkali metal ion or a lower aliphatic radical, and the use of these solutions in a process for mercerizing cellulose fibrous material.

5 Claims, 2 Drawing Figures PATENTEUJUH 17 1915 73,830,093

SHEET 1 Shrinkage 0 1'0 20 30 is 60 7'5 950 sec m PM.

PATENTEDJUH 17 1975 from/sec Shrinkage Rate 1 MERCERIZING SOLUTIONS The present invention relates to aqueous solution containing alkaline agents and phosphonic acid derivatives for mercerizing purposes.

For the purpose of mercerizing and treating cellulosic fibers, especially cotton fibers and goods made therefrom, with lyes, alkali metal hydroxide solutions having a strength sufficient to meet certain requirements are allowed to act on the material. To accelerate this operation thus assuring a continuous and economical working process, it is necessary to have the material soaked with the alkaline solution as quickly and uniformly as possible. To this effect, wetting agents are added to the solutions while making sure that these are readily soluble in the lye, bring about a maximum shrinkage rate of the cellulosic fiber within the shortest possible time and remain in solution even after the lyes have been stored for a prolonged period of time.

It is already known that alkyl sulfates, alkane sulfonates, alkyl-aryl sulfonates, lignin sulfonic acids, sulfated terpene derivatives, alkylated naphthalene sulfonic acids and analogous compounds can be used as wetting agents in mercerizing liquors. German Auslegeschrift No. 1,014,067 discloses the application of mixtures of such mono and polysulfonic acids or salts thereof in mercerizing (and lye-treating) baths. Those compounds have been obtained by sulfo-chlorination of aliphatic or cycloaliphatic hydrocarbons having to carbon atoms.

The wetting agents are generally combined with other adjuvants which disperse and keep in suspension the products which have been dissolved off the fiber during the mercerizing operation, for example cellulose degradation compounds or remaining sizes. At the same time, these adjuvants have a synergistic effect on the wetting power of the wetting agents which are known to be low-molecular-weight alcohols, for example isopropanol, butanols, alkanol-amines, glycols and derivatives thereof, polyglycols and other compounds disclosed, inter alia, in Lindner Tenside, Textilhilfsmittel, Waschrohstoffe," vol. 11, 1964, pages 1476 to 1478.

Wetting agents hitherto used for mercerizing liquors do not meet all the practical requirements at the same time. They either wet the fiber very rapidly while having to be used, however, in high concentrations or they are not stable in the alkaline solutions for a sufficiently long time, lose their effectiveness or precipitate. In many cases, moreover, their heavy foaming is trouble some.

This invention now relates to aqueous solutions for mercerizing and treating cellulosic fibers and goods made therefrom with lyes, which have an excellent wetting effect and a high stability and contain, in addition to about 10 to 400 g/l of sodium-, potassiumor lithium hydroxide or mixtures of these alkaline agents, as wetting agents. from 0.1 to 5 g/l, preferably from 1 to 5 g/l of phosphonic acid derivatives of the general formula I H (II) in which R is alkyl of 2 to 22 carbon atoms and R and R each is alkyl of 1 to 22 carbon atoms, are prepared by an addition reaction of a-olefins of 2 to 22 carbon atoms with dialkyl phosphites of the general formula Ill 0 i on on I1 (In) in which R and R are defined as above.

Dialkyl phosphites to be used for the reaction are, for example, dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, di-n-hexyl phosphite, di-Z-ethylhexyl phosphite. decyl-isobutyl phosphite, propyltetradecyl phosphite, dioctadecyl phosphite, di-eicosyl phosphite and di-docosyl phosphite.

The salts and free acids thereof may be prepared from the alkane phosphonic acid diesters by hydrolysis according to known methods.

The phosphonic acids and the salts thereof to be used according to the invention are readily soluble in water and give limpid solutions. In an alkaline medium, they have such an excellent wetting power that they can be used in lower amounts than conventional wetting agents. The concentrations used in the mercerizing solutions are between 0.1 and 5 g/l, preferably between 1 and 5 g/l, which means not only a very economical application of the compounds but also hardly any pollution of waste water. Furthermore, the phosphonic acid derivatives do practically not foam in the alkaline solutions. They are preferably used for mercerizing liquors containing a high amount of about to 300 g, preferably 200 to 250 g of sodium-, potassiumor lithium hydroxide or mixtures thereof per liter of liquor.

The known addition of lower alcohols, for example isopropanol or butanol, or of alkanol-amines, for example hutyl-diethanol-amine, to the mercerizing solutions, may further improve the wetting power of solutions.

The composition of the mercerizing solutions, for which the phosphonic acid derivatives are used according to the invention, is known; they generally contain 10 to 400 g of sodium-, potassiumor lithium hydroxide or mixtures therof per liter of liquor and, where required, further usual adjuvants. The solutions are used at temperatures of from about 0 to 25C. As to further additives, see Lindner Tenside, Textilhilfsmittel, Waschrohstoffe," vol, II, 1964, pages 1476 to 1478, and

Ullmanns Encyclopaedie der technischen Chemie, third edition, vol. 17, 1966, pages 176 to 177.

By the way, it is not necessary at any circumstances to convert the alkane phosphonic acid diesters prepared according to the prior art indicated above into the corresponding acids or alkali salts to use them according to the invention. It is also possible to add the esters directly or also after partial hydrolysis to the mercerizing solutions. since they are hydrolyzed in the alkaline liquor to yield the salts.

The mercerizing solutions of the invention are used in known manner for treating cellulosic fibers and goods made therefrom as well as textile material containing cellulosic fibers in addition to synthetic fibers.

The following Examples serve to illustrate the invention.

EXAMPLES Since the wetting power of strongly alkaline liquors cannot be measured using conventional devices according to German industrial Standards (DIN) 53,901, the following tests were carried out using, as a measure for the wetting power of a mercerizing liquor, the shrinkage of cotton in this liquor. For this purpose, a test device suitable for measuring mercerizing liquors according to Hintzmann was used. This device is described in detail in Melliand Textilberichte" (1968), No. 3, pages 311 to 315 and No. 4, pages 450 to 456. This device was operated at 20C with an amount of 250 cc. under a charge of 33 grams. Measuring was performed on cotton hanks (70/2-fold) having a length of 27.4 cm. Shrinkage was measured after a period of action of the liquor of 5, 10, 2O, 30, 45, 60, 75 and 90 seconds. The shrinkage speed in mm/sec. was calculated from the shrinkage values obtained in mm.

All the tested mercerizing liquors contained 220 g of sodium hydroxide per liter and, in addition, the following wetting agents and adjuvants:

The results in the Table convincingly demonstrate the advantage of the phosphonic acid derivatives to be used according to the invention. The results measured on liquors Nos. 1 and 1(a) show an unaltered wetting power of the mercerizing solutions of the invention even after a storage time of 24 hours.

For further illustration, the values of shrinkage and shrinkage speed are given diagrammatically by way of example in the accompanying drawings. FIG. I shows the values of shrinkage as a function of time using liquors Nos. 1, 5 and 6. FIG, II shows the corresponding values of shrinkage speed as a function of time.

We claim:

1. An aqueous mercerizing solution essentially consisting of 10 to 400 g/l of sodium-, potassiumor lithium hydroxide or a mixture thereof, and 0.1 to 5 g/l of phosphonic acid derivative of the formula in which R stands for an aliphatic linear, branched or cyclic hydrocarbon radical having 6 to 10 carbon atoms, and X and Y which may be identical or different, each stands for hydrogen, sodium, potassium or an aliphatic linear or branched hydrocarbon radical having 1 to 4 carbon atoms.

2. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of sodium methyl n-octane phosphonate.

3. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of disodium noctane phosphonate.

4. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of sodium ethyl n-octane phosphonate.

Liquors Nos. 1 and 1(a) had the same composition; liquor No. 1(a) was, however, allowed to stand for 24 hours prior to its use for the tests.

The test results are compiled in the following Table.

5. A process for treating with lyes and mercerizing cellulosic fibrous material, which comprises treating the fibrous material with an aqueous alkaline merceriz- 5 ing solution containing, as a wetting agent 0.1 to 5 g/l of a phosphonic acid derivative of the formula Shrinkage Shrinkage speed Time in mm in mm per sec. sec. Liquor No. Liquor No.

1 Hu) 2 3 5 6 l 1(a) 2 3 4 5 6 5 5 l 38 7 24 29 4 5 l 38 7 24 29 4 10 2K 1. 7l 32 66 6B 14 23 I4 33 25 42 39 IO 20 64 82 84 83 34 36 35 ll 38 l2 15 2O 30 74 72 85 77 X5 86 5] i0 22 3 7 l 3 i7 45 80 78 85 83 86 87 64 6 6 O (1 l l 13 b0 S4 81 87 84 87 88 4 3 Z l l l l l 75 H5 83 87 85 88 88 l 2 O 1 l 0 5 90 S5 87 86 88 89 84 O 2 2 l (l l 4 in which R stands for an aliphatic linear, branched or cyclic hydrocarbon radical having 6 to l0 carbon atoms, and X and Y which may be identical or different each stands for hydrogen, sodium. potassium or an aliphatic linear or branched hydrocarbon radical having I to 4 carbon atoms.

l k k 

1. AN AQUEOUS MERCERIZING SOLUTION ESSENTIALLY CONSISTING OF 10 TO 400 G/L OF SODIUM-, POTASSIUM OR LITHIUM HYDROXIDE OR A MIXTURE THEREOF, AND 0.1 TO 5 G/L OF PHOSPHONIC ACID DERIVATIVE OF THE FORMULA
 2. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of sodium methyl n-octane phosphonate.
 3. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of disodium n-octane phosphonate.
 4. An aqueous mercerizing solution as claimed in claim 1, having a content of 0.1 to 5 g/l of sodium ethyl n-octane phosphonate.
 5. A PROCESS FOR TREATING WITH LYES AND MERCERIZING CELLULOSIC FIBROUS MATERIAL, WHICH COMPRISES TREATING THE FIBROUS MATERIAL WITH AN AQUEOUS ALKALINE MERCERIZING SOLUTION CONTAING, AS A WETTING AGENT 0.1 TO 5 G/1 OF A PHOSPHONIC ACID DERIVATIVE OF THE FORMULA 